Dithiophosphonic acid amides and process for their production



United States Patent 3,018,301 DITHIOPHOSPHONIC ACID AMIDES AND PROCESS FOR THEIR PRODUCTION Gerhard Schrader, Wnppertal-Cronenberg, Germany, as-

signor to Farbenfabriken Bayer Aktiengesellschaft,

Leverkusen, Germany, a corporation of Germany No Drawing. Filed Apr. 13, 1960, Ser. No. 21,880

Claims priority, application Germany Apr. 16, 1959 14 Claims. (Cl. 2609461) The present invention relates to and has as its objects new and useful dithiophosphonic acid-ester-amides and processes for their production. The new compounds, which are highly effective insecticides, may be represented by the following general formula R1 s N My R \SR: in which R, R and R stand for aliphatic radicals and R stands for optionally substituted aliphatic radicals.

Alkyl-thionophosphonic acid amide chlorides have recently become known in the literature (cf. B. A. Arbusow. N. I. Rizpolozhenski and N. A. Svereva, Izvest. Akad. Nauk SSSR (1955) 1021-1030). According to fundamentally known processes, these chlorides or, in general, halides of this type may be reacted with alkali metal hydrogen sulfides in such a manner that the corresponding sa ts of alkyl-dithiophosphonic acid-amides are formed. The following equation may illustrate this reaction:

Hal SX In the above formulae R more specifically stands for a lower alkyl or cycloalkyl radical, R and R are preferably also lower alkyl radicals, but may also be cyclically linked with one another to form an N-containing heterocyclic ring system. Hal preferably stands for C1 or Br, and X is an alkali metal or NH.,.

By reaction of alkyl halides, which may be optionally substituted, with the aforesaid salts of alkyl-dithiophosphonic acid-amides, new esters of alkyl-dithiophosphonic acid-amides of highly insecticidal action are obtained which have not hitherto been described in the literature. The following reaction scheme may illustrate this process:

or -phosphinic-acid derivative and a (di) (thio)-carbamic- (carbonic) acid derivative. The last groups of compounds being possibly linked to the alkyl group R; by another alkoxyor alkyl-mercapto-group.

It is to be understood that instead of the aforementioned salts, the free acids may also be reacted with the optional- 1y substituted alkyl halides in the presence of a suitable acid-binding agent.

The new compounds generally are obtained in good yields. They are distinguished by a good contact-in"- secticidal and ovicidal activity whilst having a comparatively low toxicity against warm-blooded animals.

As an example for the special utility of the present invention the compounds of the following formulae (I) S N(CH=) n/ CHsP\ s-GHT-SQQ n s N on H/ a): SCH

CHa-P S-CH:--S

have been tested against aphids and spider mites. Aqueous dilutions of these compounds have been prepared by mixing the active ingredient with the same amount of dimethyl formamide as an auxiliary solvent adding thereto 20% by weight referred to active ingredient of a commercial emulsifier consisting of a benzyl hydroxy polyglycol ether containing about 10 to 15 glycol ethers, and diluting at last this premixture with water to the desired concentration indicated in the following paragral hs.

The tests have been carried out as follows:

(a) Against aphids of the type Doralis fabae: heavily infested bean plants (Vicia faba) have been sprayed drip wet with solutions as prepared above in a concentration as shown below. The effect has been determined after 24 hours by counting the dead pests either on the surface of the soil or still remaining on the plants. The following results have been obtained:

Aqueottiis codicentre on '1 Killing rate Compound 35233513 (in percent) water) (D 0.1 (II) 0.1 100 (b) Against spider mites: bean plants (Phaseolus vulgaris) of about 15 inches height are sprayed drip wet with solutions prepared as indicated above and in a concentration as shown below. The bean plants have been infested heavily with the two-spotted spider (species Tetranychus telarius). Evaluation has been carried out after 24 hours, 48 hours and 8 days. The following re- The following examples are given for the purpose of illustrating the invention and show the great variety of the process claimed herein.

Example 1 a l CHPP/ 0.001% solutions.

49 grams (0.25 mol) of the potassium salt of methyldithiophosphonic acid dimethyl amide are dissolved in 150 cc. of acetonitrile. 40 grams (0.25 mol) of ot-chloromethyl-thiophenyl ether are added at 45 C. with stirn'ng. Stirring is continued at 45 C. for an hour and the reaction product is subsequently poured into 300 cc. of ice water. The separated oil is taken up in 200 cc. of .benzene, the benzene layer separated, washed neutral with water and dried. Upon removal of the solvent by vacuum distillation, 55 grams of the new ester are obtained as a water-insoluble, pale-yellow oil. Yield 79% of the theoretical. On rats per os toxicity 25 mg./kg. LD Aphids are killed completely with 0.1 solutions. Spider mites are killed to 80% with 0.001% solutions.

By exactly the same waythere may be obtained the following compounds:

Example 2 49 grams (0.25 mol) of the potassium salt of methyl- -dithiophosphonic acid dimethyl amide are dissolved in 150 .cc. of acetonitrile. 41 grams of p-chlorobenzyl chloride ,are added at 40 C. with stirring. The product is kept at 4050' C. for an hour and then worked up as described in Example 1. 46 grams of the new ester of B.P. 118 C./0.01 mm. Hg are thus obtained. Yield 66% of the theoretical. On rats per os toxicity 100 mg./kg. LD Aphids are killed completely with 0.01%. solutions and Spider mites are killed completely with 0.01% solutions.

By exactly the same way there may be obtained the following compound:

ona-P S-CH Example 3 CHr-i .phenyl thioether are addedat 459. C. with. stirring. The

product is warmed to 50 C. for an hour and then worked up. as described in Example 1. 57 grams of the new ester are obtained as a pale-yellow, water-insoluble oil.

Yield 73% of the theoretical. On rats per os toxicity 100 v mg./kg. LD Aphids are killed completely with 0.1% solutions and spider mites are killed completely with 49 grams (0.25 mol) of the potassium salt of methyldithiophosphonic acid dimethyl amide are dissolved in 150 cc. of methyl ethyl ketone. '28 grams of a-ChlOI'O- methyl-thioethylether are added at 50 C. with stirring.

The product is kept at 50 C. for an hour and then worked up in usual manner. 34 grams of the new ester of B.P. 74 C./0.01 mm. Hg are obtained. Yield 60% of the theoretical. On rats per os toxicity 10 mg./kg. LD Aphids are killed-completely with 0.1% solutions and spider mites are killed to with 0.001% solutions.

By exactly the same way there may be obtained the following compounds:

S-CHPBCIH! '8 N H 6 ll/ L :-P

s em-sous. E ic ample 5 Y s we GE's-P v S-CH:CN I v 49 grams (0.25 mol) of the potassium salt ofmethy dithiophosphonic acid dimethyl amide are dissolved in cc. of methyl ethyl ketone. 22 grams (0.25 mol) of achloroacetonitrile are added at 45 'C. with stirring. The product is warmed to 50 C. for one hour and then worked'up in usual manner. 35 grams of the new ester of B.P. 86 C'./0.01 mm. Hg are thus obtained. Yield 72% of the theoretical. 0n rats per os toxcity 25 mg./kg. LD Aphids are killed completely with 0.1% solutions and spider mites are-killed completely with 0.01% solutions.

Example 6 S' N(CH:)2

S-CHr-COOCzH:

49 grams (0.25 mol) of the potassium salt of methyldithio-phosphonic acid dimethyl amide are dissolved in 150 cc. of acetronitrile. 31 grams of chloroacetic acid ethyl ester are added at 45 C. with stirring. The product is warmed to 50 C. for an hour and then worked up in wer CHI

49 grams (0.25 mol) of the potassium salt of methyldithiophosphonic acid dimethyl amide are dissolved in 150 cc. of acetonitrile. 47 grams (0.25 mol) of l-methylmereapto-4-methyl-6-benzyl chloride are added at 80 C. with stirring. Heating is continued at 80 C. for an hour and the product then worked up in usual manner. 64 grams of the new ester are thus obtained as a yellow, water-insoluble oil. Yield 84% of the theoretical. On rats per os toxicity 25 mg./kg. LD Aphids are killed completely with 0.1% solutions and spider mites are killed completely with 0.001% solutions.

By exactly the same way there may be obtained the following compound:

S N(CH) n/ H CHs-P S-CH SCzHs s-cm-oo 49 grams (0.25 mol) of the potassium salt of methyldithiophosphonic acid. dimethyl amide are dissolved in 150 cc. of acetonitrile. 39 grams of w-chloro-acetophenone, dissolved in 50 cc. of acetonitrile, are then added at 45 C. with stirring. The temperature is kept at 50 C. for one hour and the product then worked in usual manner. 40 grams of the new ester are obtained as a water-insoluble, yellow oil. Yield 58% of the theoretical. On rats per os toxicity 50 mg./kg. LD Aphids are killed completely, with 0.1% solutions and spider mites are killed to 90% with 0.01% solutions.

By the same way there may be obtained the following compound:

CHr-P Example 9 (cHmN s s N(OH:):

P-SCHr-SP CH: CH:

78 grams (2/5 mol) of the potassium salt of methyld'rthiophosphonic acid dimethyl amide are dissolved in 150 cc. of acetonitrile. 35 grams (0.20 mol) of methyl-' 78 grams (2/5 mol) of the potassium salt of methyldithiophosphonic acid dimethyl amide are dissolved in 150 cc. of acetonitrile. 27 grams (1/5 mol) of u,a'-dichloromethylthioether are added at 80 C. with stirring. The temperature is kept at 80 C. for an hour and the product is then worked up in usual manner. 32 grams of the new ester are thus obtained as a pale-yellow, waterinsoluble oil. Yield 44% of the theoretical. On rats per os toxicity 25 mg./kg. LD Aphids are killed to 50% with 0.1% solutions and spider mites are killed completely with 0.01% solutions.

98 grams (0.5 mol) of the potassium salt of methyldithiophosphonic acid dimethyl amide are dissolved in 200 cc. of acetonitrile. 29 grams of a,a'-dichloromethyl ether are added at 60 C. with stirring. The temperature is kept at 60 C. for. a further hour and the product then worked up in usual manner. 58 grams of the new ester are thus obtained as a water-insoluble, pale-yellow oil. Yield 66% of the theoretical. On rats per os toxicity 5 mg./kg. LD 0.1% solutions kill aphids to and spider mites are killed to with 0.01% solutions.

Example 12 N( s): am-P S-CH2-SO2H5 52 grams (0.25 mol) of the potassium salt of ethyldithiophosphonic acid dimethyl amide are dissolved in cc. of. acetonitrile. 28 grams of a-chlorornethyl-thioethyl ether are added at 45 C. with stirring. The product is kept at 50 C. for a further hour and then worked up in usual manner. 43 grams of the new ester of B.P. 80 C./0.01 mm. Hg are thus obtained. Yield 71% of the theoretical 0.01% solutions kill aphids to 100% and spider mites to 90%.

In a similar manner the following compounds may be obtained:

water-insoluble pale-yellow oil yield 82% of the theoretical S N(CHs)2 B.P. 128 C./0.01 mm. Hg yield 73% of the theoretical S-CH2C O O CzHs B.P. 84 C./0.01 mm. Hg yield 82% of the theoretical S N(CHs)a C:HsP

S-CH

SICHa water-insoluble, yellow oil yield 83% of the theoretical S N C H3) C2H5-P water-insoluble, pale-yellow oil yield 78% of the theoretical B.P. 87 C./0.01 mm. Hg yield 74% of the theoretical S N(CHa)a s-orn-cnr-soma 52 grams (0.25 mol) of the'potassium salt of ethyldithiophosphonic acid dimethyl amide are dissolved in 150 cc. of acetonitrile. 32 grams (0.25 mol) of p-chloroethyl-thioethyl ether are added at 80 C. with stirring.

The temperature is kept at 80 C. for an hour and the product is then worked up in usual manner. 47 grams of the new ester of B.P. 91 C./0.0l mm. Hg are thus obtained. -Yield 73% of the theoretical. Aphids are killed completely with 0.1% solutions. Spider mites are killed to 70% with 0.001% solutions.

Example 14 [Bi/NT CH3) 2 CzHs-P B.P. 92 C./0.01 mm. Hg yield 73% of the theoretical S N( a)a CaHPI E V S-CH-CHa-SCzHs B.P.'98 O./0.01 mm. Hg yield 70% of the theoretical S N(CH:): ll/ ms-P S-CHz-CHa-CN B.P. 106 O./0.01 mm. Hg 69% of the theoretical I claim: l. The compound of the following formula s more).

CHPI E 2'. The compound of the following formula S N(CH3):

CH3.P

, eeme V substituted benzyl,

3. The compound of the following formula s more CHs-i S-CHz-CN 7 4. The compound of the following formula S N(CH3)2 ll/ CHa-P s -CH:C o 0 01B: 5. The compound of the following formula CH3 CH: 6. The compound of the following formula S-CHz-CHrSCaH; 7. The compound of the following formula 8 Mom),

C2Ha- SCH2CH2-N(C2H$)a 8. A dithiophosphonic acid ester amide of the following general formula in which R stands for a member selected from the group consisting of lower alkyl and cyclohexyl radicals, R and R each stand for lower alkyl radicals and when taken together with -N stand for a member selected from the group consisting of piperidino and morpholino; and R stands for a member selected from the group consisting of a phenyl-mercapto-substituted lower alkyl radical, a lower alkyl-mercapto-substituted lower alkyl radical, a lower dialkyl-amino-substituted lower alkyl radical, a lower alkoxy carbonyl-substituted lower alkyl radical,-a lower dialkyl amino-carbonyl-substituted lower alkyl radical, a cyano-substituted lower alkyl radical, a phenylcarbonyl-substituted lower alkyl radical, benzyl, chlorolower alkyl-mercapto-substituted benzyl, lower alkyl-mercapto-substitutedlower alkylsubstituted benzyl, another ll 12-? R:

S -substitued lower alkyl radical,

another Wk 12-]? R: s -lower alkylene-S-substituted lower alkylene radical and another Wk 12-]? a I R:

8 -lower alkylene-O-suhstitnted 9 stand for a lower alkyl radical and R stands for a lower alkyl-mercapto lower alkyl radical.

11. A compound of claim 8 wherein R, R and R each stand for a lower alkyl radical and R stands for a cyano lower alkyl radical.

12. A compound of claim 8 wherein R, R and R, each stand for a lower alkyl radical and R stands for a lower alkoxy carbonyl-substituted lower alkyl radical.

13. A compound of claim 8 wherein R, R and R each stand for a lower alkyl radical and R stands for a lower 10 dialkyl-amino lower alkyl radical.

10 14. A compound of the following formula R1 R4 \N s s N/ 111 i s-A1k-xA1k-s-i \RS in which R, R R R and R, are each a lower alkyl radical and X stands for a chalcogeu having an atomic weight from 16 to 33.

No references cited. 

8. A DITHIOPHOSPHONIC ACID ESTER AMIDE OF THE FOLLOWING GENERAL FORMULA 